Light sensitive silver halide materials containing yellow-forming couplers



Dec. 29, 1970 MAKQTO 0s EI'AL 3,551,156

LIGHT SENSITIVE SILVER HALIDE MATERIALS CONTAINING YELLOW-FORMINGCOUPLERS- Filed Jan. 25. 1967 OPTICAL DENSITY WAVE LENGTH(ml-l) OPTICALDENSITY WAVE LENGTH(mn) INVENTORS MAKOTO YOSHIDA MOMOTOSHI TSUDA KAZUYASANO YASUSHI OISHI BY L/ V Se02//zes-&/5emmes" ATTORNEYS United StatesPatent Otfice 3,551 ,156 Patented Dec. 29, 1970 LIGHT SENSITIIE SILVERHALIDE MATERIALS CONTAINING YELLOW-FORMING COUPLERS Makoto Yoshida,Momotoshi Tsuda, Kazuya Sano, and

Yasushi Oishi, Kanagawa, Japan, assignors to Fuji Shashin FilmKabushilri Kaisha, Ashigara-Kamigun,

Kanagawa, Japan, a corporation of Japan Filed Jan. 23, 1967, Ser. No.611,066 Claims priority, applicatiorglsgapan, Jan. 24, 1966,

7 Int. Cl. G03c 1/40 US. Cl. 96-100 5 Claims ABSTRACT OF THE DISCLOSUREThe novel yellow-forming coupler having a lower alkoxyl group at thebenzoyl nucleus and a halogen atom at the anilide group of a benzoylacetoanilide, and shown by NIICOR has been found to have a high couplingreactivity and a sufficient solubility in organic solvents as well as toprovide a yellow image of excellent fastness and a spectral absorptionsuitable for color photography.

BACKGROUND OF THE INVENTION The following three methods of incorporatinga diffusion resistant coupler in a photographic emulsion layer havehitherto been known:

(1) Water solution method: neutral or alkaline aqueous solution of thecoupler carrying a carboxyl group or a sulfonic acid group, is addedinto the emulsion and the mixture neutralized if needed.

(2) Oil-solution method: The coupler is dissolved in an organic solvent,dispersed into an aqueous medium to fine colloidal particles and thenadded into the emulsion.

(3) A coupler melt is added into the emulsion directly or in the form ofaqueous dispersion.

In order to constitute a blue sensitive emulsion layer by use of ayellow-forming coupler of the oil-solution type, it is required that thecoupler have a high coupling reactivity with the oxidation product ofthe developing agent, that the yellow dye image formed by colordevelopment have a light absorption adapted for the color reproduction,and that the yellow dye stands severe storing conditions, and that thecoupler have no bad influence upon the photographic emulsion.Furthermore, the coupler must be easily dissolved in the organic mediumused and must not crystallize during storage.

Since the commonly used yellow-forming couplers of the oil-solution typedo not have high coupling reactivities against the oxidation product ofa developing agent in the dispersed state in the emulsion layer, a bluesensitive emulsion layer having excellent photographic characteristichas been difficultly obtained in such a system. The change in thechemical structure of a yellowforming coupler (such as a substitutedbenzoylacetanilide) as would impart high coupling reactivity to it tendsto shift the spectral absorption of the resulting yellow dye to thelonger Wave length, causing the increase of the green absorption whichis not desirable from the view point of color reproduction. That is tosay, it has been believed that a general inconsistent relationshipexists between the desired light absorption of a yellow-forming Couplerand its coupling reactivity.

Moreover, the dye image from the known yellowforming coupler tends tofade, in particular, under exposure to a strong light for a long time,which is a great obstacle for the long preservation of colorphotographs. In the field of color photography, therefore, a number ofefforts have been made to obtain a yellow-forming coupler having a highcoupling reactivity, and giving a lightdurable yellow image withoutgreen absorption.

SUMMARY OF THE INVENTION This invention relates to novel light sensitivematerials for color photography, in which yellow-forming couplers areincorporated. In the substrative process of color photography, cayn,magenta and yellow dyes are formed during development of silver halideby coupling of the oxidation product of a developing agent such asN,N-disubstituted-p-phenylene-diamine with suitable couplers.

In the system where spectrally sensitized silver halide emulsionscontain the corresponding couplers, the couplers have to be maderesistant to diffusion in order to prevent deterioration of colorreproduction due to diffusion of the couplers through the layers. It isnecessary, therefore, to introduced in the coupler molecule ballastgroups having ten or more carbon atoms serving to render itindiffusible.

DESCRIPTION OF THE DRAWINGS FIG. 1 is a spectral absorption curve of theethyl acetate solution of the yellow dye from anisoylaceto-(Z-chloro-5-(2,4-di-tert amylphenoxyacetamide)) anilide, a coupler of thegeneral Formula I (Curve A); and

FIG. 2 relates to Example 3 and is the spectral absorption curve of theyellow image.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In accordance with the presentinvention, there is provided a light sensitive material for colorphotography, containing a novel yellow-forming coupler represented bythe general formula,

NHCOR I C (I) wherein X is a halogen atom, Y is an alkoxyl group of 13carbon atoms and -COR is an acyl group of 9-28 carbon atoms.

The foregoing novel coupler used in this invention has a high couplingreactivity and sufficient solubility in organic solvents, and it gives ayellow image of excellent fastness and spectral absorption for colorreproduction. The color photographic material produced by the use ofthis novel coupler is characterized by good photographic propertiesconcerning sensitivity, gradation and image quality as well as by theease of production, the photographic image obtained from this materialbeing adequately stable even under severe conditions. Other merits orfeatures of the invention will be hereinafter illustrated.

The new couplers of our invention, represented by the general Formula I,exhibit a similar or even high coupling reactivity in comparison withthe known couplers having the highest coupling reactivity as arerepresented by the following general Formula II where X and COR have thesame meaning as in I. In addition, the dyes formed from them exhibitmuch less green absorption undesirable from the standpoint of colorreproduction of the subtractive process. Thus, a less reddish, sharpyellow image can be obtained.

NHCOR In this general formula, X and COR have the same meaning in thegeneral Formula I.

In FIG. 1 are shown the spectral absorption curve of the ethyl acetatesolution of the yellow dye from anisoylaceto-(2-chloro-5-(2,4-di-tertamylphenoxyacetamide) anilide, a coupler of the general Formula I (CurveA) to be compared with that of another yellow dye from benzoyl-(2-chloro-5-( 2,4-tert-amylphenoxyacetamide) )anilide, a known couplerof the general Formula II (Curve B).

FIG. 1 shows that the former curve is steeper to the longer Wave lengththan the latter, resulting in less green absorption over 500millimicrons. It is evident from these results that the colorphotographic material of our invention gives a high blue sensitivity,yellow density and good gradation, while giving a less reddish hue.

Furthermore, the novel coupler of the invention has such a feature thatthe yellow image obtained is not only durable to attacks of heat andhumidity, but fades to a much less extent even under exposure to astrong light. Consequently, a photograph obtained by developing thecolor photographic material of this invention can be preserved undersevere conditions.

To the incorporation of the coupler of this invention into aphotographic emulsion, various procedures can be satisfactorily applied,typical of which are the followings.

(a) Dissolving the coupler in a less water-soluble, less volatilesolvent (B.P. 200 C. or more), dispersing the resulting coupler solutionin an aqueous medium, emulsifying and then adding it to the emulsion.Di-in-butyl phthalate, tricrsyl phosphate and N,N-di-ethylcaproic acidamide are examples of such organic solvents.

(b) Dissolving the coupler in a low boiling, relatively water-insolublesolvent, dispersing the resulting solution in an aqueous medium andadding it to the emulsion. The organic solvent used is removed offduring the later steps. Ethyl acetate, cyclohexanone or tetrahydrofuranis used as such a solvent.

(c) Dissolving the coupler in a water-miscible organic solvent andadding the resulting coupler solution to a photographic emulsion. Thecoupler is dispersed in the emulsion as fine colloidal particles. Thesolvent used may be either removed during the following step of makingthe photographic material, or retained in the emulsion layer.Illustrative of such solvent are dimethyl-formamide, dimethylsulfoxide,N-methylpyrrolidone and glycerine.

The dispersion of the coupler can be facilitated by using a mixture ofsuch solvents as given in (a), (b) and depending on the solubility ofthe coupler used.

CHuO

CH", O

OOOHzCONH- cum-@ooomo ONII GOCHzC ONE-- In order to make up a bluesensitive photographic emulsion layer having excellent properties, itdoes not matter whether only one of the couplers represented by thegeneral Formula I is used or two or more of them are used, or whether ayellow-forming coupler not represented by the general Formula I arejointly used. As occasion demands, a yellow-forming coupler ofwater-soluble type may be jointly used in the same emulsion layer.

When the yellow-forming coupler represented by the general Formula I isused together with a cyanor magenta-forming coupler in the same emulsionlayer, the color reproductivity can be improved, as disclosed inJapanese patent publication No. 391/1965.

The coupler of this invention can be satisfactorily applied to variouscolor photographic materials, for example color printing paper, colorpositive film, color negative film and color reversal film.

Our invention is applicable not only to color photographic materials ofthe so-called multi-layer type where two or more emulsion layers eachcontaining spectrally sensitized silver halide and the correspondingnonditfusing coupler are superposed on one support, but also, to theso-called mixed grain type material where two or more kinds of finegrains each containing spectrally sensitized silver halide and thecorresponding nondiffusing coupler are mixed and coated on one support.

The yellow-forming coupler of this invention has been expressed by theforegoing general Formula I in which COR is an acyl group of 928 carbonatoms.

Those carrying less than 9 carbon atoms partly go into the alkalinedeveloping solutoin and diffuse into other layers resulting in worseningof the color reproductivity, since the aggregation force within thecoupler molecules or between the coupler molecule and solvent moleculeis insufficient. On the other hand, when the number of carbon atomsexceeds 28, the blue extinction per weight (i.e., volume) of the yellowdye formed becomes too small for the emulsion layer to keep the bluedensity sufi'lcient without increasing the thickness of the emulsionlayer.

In the foregoing general Formula I, it is the most desirable from thestandpoint of the coupling reactivity and solubility of the coupler andthe absorption of the resulting dye that the substituent NHCOR ispositioned at the 4- or better at 5-position of the 2-halogen-anilidenucleus.

The typical examples of the couplers used in the present invention areas follows, but the invention is not to be limited thereby.

I 3 C Hu (tort) NHCOCH2O -C5Hn (sec) CO(OH2)HCH3 i nooonzonm l orCO(CH2)14CH13 Q-mrooomonm I l U II11 (tort) Examples of synthesizingsome of these compounds will be given. Example of synthesis (1):synthesis of compound (1) (a) Synthesis ofanisoylaceto-(2-chloro-5-nitro)anilide; 100 g. of2-chloro-5-nitroaniline and 127 g. of ethyl anisoylacetate were heatedin an oil bath at 160 C. for 1.5 hours. The reaction mixture wascrystallized in methanol and reprecipitated fromdimethylformamide-methanol.

(b) Synthesis of anisoylaceto'Q-chloro amino) anilide; 85 g. of thenitro-compound obtained in (a) was mixed with 50 g. of reduced ironpowder and 1.2 l. of ethanol, to which 225 ml. of acetic acid and 200ml. of water were added dropwise within 2-3 minutes After stirring for30 minutes, 300 ml. of the ethanol was distilled 01f. 500 ml. of ice wasadded to remove insoluble contaminants. Caustic soda was added to adjustpH to 11, then water was added to 1000 ml. in order to remove ironhydroxide. Reprecipitation followed by recrystallization were done fromacetic acid and ethanol respectively. 51 g. of an amino-compound meltingat 146 C. was obtained.

Synthesis of compound (1); 10 g. of the aminocompound obtained in (b)was mixed with 10 g. of 2,4- di-tert-amylphenoxyacetyl chloride, 10 ml.of pyridine and 30 ml. of acetone and heated on a water bath. After 1hour, the half amount of the acetone was distilled 01f and the solutionwas poured into water, and the aqueous phase decanted. Methanol wasadded for crystallization. Recrystallization from ethanol gave 12 g. ofcompound (1) melting at 140 C.

Example of synthesis (2): synthesis of the compound (2) 10 g. of theamino-compound obtained in (b) of the foregoing example was suspended in100 ml. of acetonitrile, to which 5 g. of triethylarnine was then addedand g. of 2,4-di-sec-amylphenoxyacetyl chloride was dropped in the formof a solution in 20 ml. of acetonitrile with stirring at roomtemperature. Stirring was further continued for 20 minutes and thetriethylarnine salt formed was filtered off. The mixture was poured intowater, the aqueous phase decanted, and the residue was crystallized byuse of methanol and recrystallized from ethanol. 9 g. of compound (2)melting at 110 C. was obtained.

Example of synthesis (3): synthesis of the compound (3) 43 g. of theamino'compound obtained in (b) of example of synthesis (1) was suspendedin 300 ml. of acetone, to which 16 g. of triethylarnine was added andinto this suspension a sufliciently degassed acid chloride from 53.5 g.of 3 (N-butylhexadecanamide)-propionic acid (cf. Japanese Pat. 427,977entitled Color photographic material) and 19 g. of thionyl chloride wasdropped with ice-cooling and stirring in the form of a solution in 50m1. of acetone. After dropping, stirring was continued for 20 minutes,and the triethylarnine salt was filtered oif. After acetone wasdistilled off, the mixture was poured into Water, and the aqueous phasewas decanted. Crystallization in methanol followed by recrystallizationfrom ethanol gave 24 g. of a crystalline material melting at 955 C.

Example of synthesis (4): synthesis of compound (4) (2.) Synthesis ofanisoylaceto-(2-chloro 4 nitro) anilide; 172.5 g. of2-chloro-4-nitroaniline and 222 g. of ethyl anisoylacetate were heatedin an oil bath at 160 C. for 1.5 hours. The reaction mixture wascrystallized in methanol and reprecipitated fromdimethylformamidemethanol. 80 g. of the compound melting at 1578 C. wasobtained.

(b) Synthesis of anisoylaceto-(Z-chloro 4 amino) anilide; into themixture consisting of 40 g. of the nitrocompound obtained in (a), 50 g.of reduced iron powder and 150 ml. of ethanol were added 250 ml. ofacetic acid and 200 ml. of water dropwise. The mixture was treated inthe similar manner to (b) of example of synthesis (1) and wasrecrystallized to give 18 g. of crystals melting at 145-7 C.

c) Synthesis of the compound 4); 31 g. of the aminocompound obtained in(b), 500 ml. of acetone andg. of triethylarnine were mixed together, towhich the sufficiently degassed acid chloride from 38 g. of3-(N-butylhexadecanamide)-propionic acid and 13 g. of thionyl chloridewas added dropwise in the form of a solution in 100 ml. of acetone.Stirring was continued for minutes longer and the mixture was pouredinto ice water, the resulting oily product being allowed to stand forone night to yield a solid material. Recrystallization from acetonitrileand then from methanol gave 15 g. of the compound (4) melting at 109-110 C.

The following examples are given in order to illustrate the embodimentsof our invention.

EXAMPLE 1 15 g. of coupler 1), 20 ml. of di-n-butyl phthalate and 30 ml.of cyclohexanone were heated together at 60 C. to prepare a solution,which was then added to 300 ml. of an aqueous solution containing g. ofgelatin and 1 g. of sodium dodecylbenzenesulfonate and maintained at 60C. This was stirred vigorously by means of a homog enizer for minutes.The coupler was finely emulsified with the solvent.

All the emulsified dispersion was mixed with 500 g. of photographicemulsion containing g. of silver iodobromide and g. of gelatin, to which30 ml. of a 3% acetone solution of triethylene phosphoramide was addedas a hardener, and the pH was adjusted to 7.0. The resulting emulsionwas applied to cellulose film base to be 8.O 10 cm. thick on dry base.

A sharp yellow image obtained by exposing and processing of the obtainedfilm according to the following procedures.

7 (I) Color developing treatments Minutes (1) color development at 21 C.10 (2) rinsing at 21 C. 1 (3) first fixing at 21 C. 4 (4) rinsing at 21C. 3 (5) bleaching at 21 C. 3 (6) rinsing at 21 C. 2 (7) second fixingat 21 C. 3 (8) rinsing at 18 C. 20

(II) Color developing solution A (pH: 10.5

Water1000 ml.

4 amino 3 methyl-N,N-diethylaniline hydrochloride2.5 g.

Sodium sulfite (anhydrous)-l g.

Sodium carbonate (monohydrate)47 g.

Potassium bromide2 g.

(III) Fixing solution (pH=4.5)

Waterl000 ml. Sodium thiosulfate (hexahydrate)80 g. Sodium sulfite(anhydrous) g. Borax6 g. Glacial acetic acid-4 ml. Potassium alum7 g.(1V) Bleaching bath (pH=7.2)

Water1000 ml. Potassium ferricyanate--100 g. Boric acidl0 g. Borax-5 g.

EXAMPLE 2 10 g. of the coupler (2), 5 ml. of tricresyl phosphate and ml.of ethyl acetate were heated at 60 C. to prepare a solution, which wasthen added to 100 ml. of an aqueous solution containing 0.5 g. of sodiumhigher-alkylsulfonate and .7 g. of gelatin at 60 C. and vigorouslystirred by means of a homogenizer. The coupler was finely dispersed withthe solvent.

All the emulsified dispersion was mixed with 540 g. of a blue sensitivephotographic emulsion containing g. of silver chlorobromide, g. ofgelatin, 30 ml. of a 3% acetone solution of triethylene phosphoramide asa hardening agent, and 7 g. of polyvinylpyrrolidone, and then applied tobaryta paper to be a first layer of 4 10 cm. in thickness on dry base.

A green sensitive photographic emulsion containing emulsified dispersionof the coupler (a) represented by the following structure was furtherapplied thereto as a second layer, and a red sensitive photographicemulsion containing an emulsified dispersion of the coupler (b) wassuperposed as a third layer.

CzaHnC O /NCH2CH2C ONH(H3-(I1Hz 041-157 N 0 0 Coupler (a) I -c ONHCmIIwCoupler (b) The so obtained color printing paper was subjected to wedgeexposure to blue light and then to developing treatments similar toExample 1 except that the color development was carried out at 21 C. for12 minutes by use of the following developing solution.

(V) Color developing solution B Water-l000 ml. Sodium sulfite(anhydrous)2 g. N-hydroxyethyl-N-ethyl p phenylenediamene sulfate-4.5 g.Potassium carbonate-75 g. Tribasic potassium phospliate10 g. Potassiumbromide2 g. Hydroxylamine hydrochloride-2 g.

The resulting sharp yellow image exhibited a good sensitivity, gradationand maximum density required for color printing papers. The yellow of acolor print obtained from this color printing paper hardly faded evenafter a long period of exposure.

EXAMPLE 3 (i) Film K: 15 g. of the coupler (3) of our invention, 20 ml.of di-n-butyl phthalate and 30 ml. of ethyl acetate were heated at 60 C.to prepare a solution, which was added to 300 ml. of an aqueous solutioncontaining 25 g. of gelatin and l g. of sodium dodecylbenzenesulfonateat 60 C. and vigorously stirred for 30 minutes by means of ahomogenizer. The coupler was finely emulsified or dispersed with thesolvent.

All the emulsified dispersion was mixed with 500 g. of a photographicemulsion containing g. of silver iodobromide and g. of gelatin, to which30 ml. of a 3% acetone solution of triethylene phosphoramide was addedas a hardening agent, and the pH was adjusted to 7.0. The resultingemulsion was applied to cellulose acetate film base to be 80x10 cm.thick on dry base.

The film K was exposed and developed in the similar manner to Example 1to give a sharp yellow image. The spectral absorption curve of theyellow image is shown in FIG. 2.

(ii) Film L: Film L was obtained in the similar manner to the film Kexcept that the known coupler (c) of the following formula which isincluded in the general Formula II was used in place of theyellow-forming coupler (iii) Film M: 15 g. of a yellow-forming coupler(d) having the following formula was dissolved in the mixture of 100 ml.of distilled water, 15 ml. of methanol and 50 ml. of l N caustic sodasolution to prepare a solution, which was then added with stirring to500 g. of a photographic emulsion containing 45 g. of silver iodobromideand 50 g. of gelatin. 90 ml. of a 3% aqueous solution of saponin and a10% aqueous solution of citric acid in an amount sufficient to adjustthe pH to 7.0 were added thereto and the resulting emulsion, dilutedwith 200 ml. of water, was applied to cellulose triacetate film base tobe 8.0 10 cm. thick on dry base.

Coupler (c) CIIOOH l C O OH Coupler (d) The above mentioned three kindsof films L, K and M were subjected to the developing treatments similarto Example 1 to give yellow images. After the films thus processed werekept at a constant temperature and humidity vessel at C. and RH thelowering of ex- 9 10 tinction was measured with the yellow image. Theresults the coupler of our invention (3) yields yellow images are shownin Table 1. more resistant to intense exposure, as compared with the 1commonly used couplers in the prior art. TABLE 1.DEGREE OF FADING DUE TOHEAT AND We 9 HUMIDITY 5 1. A light-sensitive materlal for colorphotography, lPercent, rand of density lowering to initial density]comprising a support bearing thereon a silver halide emul- Presewationpeflod sion layer containing at least one yellow-forming couplerrepresented by the general formula Coupler day days days 20 days NHCOR o0 a 4 10 0 2 4 5 Y @ooomoorrn Q 0 35 65 I It will be understood fromthese data that the coupler wherein X represents a halogen atom, Yrepresents an (3) of our invention yields a yellow image strongly re- 15alkoxy group having 1 to 3 carbon atoms and -COR sistant to attack ofheat and humidity. represents an acyl group having 9 to 28 carbon atoms.

The three kinds of the film L, K and M developed in 2. A light-sensitivematerial as claimed in claim 1, the similar manner to Example 1, wereexposed to strong wherein said yellow-forming coupler is represented bythe light from Xenon lamp for hours and the lowering of formulalTIHCOCHzO- 05H (tort) omo-QcoomoomnQ otnn (tert) 3. A light-sensitivematerial as claimed in claim 1, wherein said yellow-forming coupler isrepresented by the 30 formula NHCOCH20C5HH (Sec) ornoQ-ooomcorm-Q JtHn(see) 4. A light-sensitive material as claimed in claim 1, wherein saidyellow-forming coupler is represented by the formula CO(CH2)14CH3NHGOCHtOHiN CAHQ oHflQ-ooomoomr-Q 5. A light-sensitive material asclaimed in claim 1, wherein said yellow-forming coupler is representedby the v formula /C 0 (CH2) 140B; GH OC 0 onto ONE-@NH o o CH2CHzN\ I:C4H9 extinction of the yellow image was measured. The results ReferencesCited are Shown 111 Table UNITED STATES PATENTS TABLE 2-DEGREE 0F FADINGDUE To 2,407,210 9/1946 Weissberger et al 96-100 LIGHT lPercent, ratioof logggiil ]of density to initial OTHER REFERENCES Initial densityBrown et al., Journal American Chemical Society, vol. Coupler W 79, pp.2919-27, (1957). Filni 13 m I. TRAVIS BROWN, Primary Examiner K: I 23 isM. i i 45 US. (:1. X.R.

It will apparently be understood from these data that

